Process for augmenting or enhancing the aroma of detergent using derivatives of cis-3-hexenol

ABSTRACT

Described is a process for augmenting or enhancing the aroma of solid or liquid anionic, cationic or nonionic detergent comprising the step of intimately admixing with a solid or liquid anionic, cationic or nonionic detergent base an aroma augmenting or enhancing quantity of at least one substrate selected from the group consisting of: 
     A. A composition of matter consisting essentially of cis-3-hexenal, cis-3-hexenyl-cis-3-hexenoate, trans-2-hexenal, and cis-3-hexenol; 
     B. A composition of matter consisting essentially of cis-3-hexenal, cis-3-hexenyl-cis-3-hexenoate, cis-3-hexenyl formate and trans-2-hexenal; 
     C. A composition of matter consisting essentially of cis-3-hexenal, cis-3-hexenyl-cis-3-hexenoate, cis-3-hexenol, cis-3-hexenyl formate and trans-2-hexenal; and 
     D. Cis-3-hexenyl methyl ether.

This Application is a Divisional of Application for United StatesLetters Patent Ser. No. 085,707 filed on Oct. 17, 1979, now U.S. Pat.No. 4,241,098 issued on Dec. 23, 1980.

BACKGROUND OF THE INVENTION

The present invention relates to cis-3-hexenyl derivatives having thegeneric structure: ##STR1## wherein R is one of the moieties: ##STR2##produced by the novel processes of our invention and to novelcompositions using one or more of such cis-3-hexenyl derivatives toaugment, modify or enhance the flavor and/or aroma of consumablematerials or impart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (on in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Sweet, deep green, crushed leaf-like, fruity, pear-like, greenapple-like, fresh fig-like, winey and white grape-like aroma and flavornotes are particularly desirable in many foodstuff flavors, chewing gumflavors, toothpaste flavors and medicinal product flavors, particularlyin the oral hygiene area.

Powerful green, leafy, fruity, fatty and spicy aromas with strongcrushed green undertones are desirable in several types of perfumecompositions, perfumed articles (e.g. anionic, cationic and nonionicdetergents and dryer-added fabric softener articles) and colognes.

Sweet, fruity, cooling and green aromas and tastes are desirable inconnection with augmenting or enhancing the flavors or aromas of smokingtobaccos both prior to smoking and on smoking in both the mainstream andthe sidestream.

The book "Perfume and Flavor Chemicals (Aroma Chemicals)" by StephenArctander at Monograph 1598 discloses cis-3-hexenal to have a powerfuldeep green, leafy odor reminiscent of strawberry leaf and wine leaf,freshly crushed. Arctander further states that cis-3-hexenal isoccasionally used in perfume compositions as part of a "green" topnotecomplex not only for herbaceous fragrance types but also in variousfloral compositions. The concentrations, Arctander states, will normallybe less than 0.1% in the perfume oil. Arctander further states thatcis-3-hexenal is used in flavor compositions in minute traces tointroduce a natural green note in many types of fruit flavors. Arctanderstates that concentrations in the finished product of cis-3-hexenal maybe about 0.2 to 0.5 ppm. Cis-3-hexenal is stated to be produced byoxidation of hexenol and is on the GRAS list as FEMA No. 2561. Prior toour invention, however, the difficulty with using cis-3-hexenal was thatit easily decomposes in the presence of oxygen. Thus a more stable formof cis-3-hexenal has been desired in the flavor and fragrance industriessince the discovery of said cis-3-hexenal several decades ago.

Kajiwara, Harada and Hatanaka indicated that cis-3-hexenal may beisolated from tea leaves (Thea Sinensis) in Agr. Biol. Chem., 39 (1),243-247, 1975. It was indicated by Kajiwara et al, that cis-3-hexenalcan be produced by oxidizing cis-3-hexenol using chromium oxide-pyridinemixture in the presence of methylene dichloride ordimethylsulfoxide-phosphorous pentoxide mixture.

Such oxidizing agents as pyridinium chlorochromate having the structure:##STR3## have never been disclosed to be useful in oxidizingcis-3-hexenol to produce cis-3-hexenal in admixture with other compoundswhereby the mixture is stable particularly with respect to thesubstantivity of the cis-3-hexenal. The pyridinium chlorochromate havingthe structure: ##STR4## has, however, been disclosed as an oxidizingagent by Corey and Suggs in Tetrahedron Letters No. 31, pages 2647-2650,1975 ("Pyridinium chlorochromate. An Efficient Reagent for Oxidation ofPrimary and Secondary Alcohols to Carbonyl Compounds"). 1-Heptanol isdisclosed to be able to be oxidized to heptanal using pyridiniumchlorochromate, by Corey and Suggs. Also, citronellol is disclosed byCorey and Suggs to be able to be oxidized to citronellal in a 82% yieldusing pyridinium chlorochromate.

Japanese published patent application No. J5 4012 309 discloses3-hexynyl-alkylethers as long lasting perfuming agents and useful as anintermediate for the synthesis of cis-3-hexenyl ethers or pheromones.Japanese patent disclosure No. J5 4012 309 does not, however, disclosethe unobvious, unexpected and advantageous organoleptic properties ofcis-3-hexenyl methylether.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 sets forth the GLC profile for the reaction product of Example I.

FIG. 2 sets forth the GLC profile for the reaction product of ExampleII.

FIG. 3 sets the NMR spectrum for cis-3-hexen-1-ol produced according toExample II.

FIG. 4 sets forth the mass spectrum for cis-3-hexen-1-ol producedaccording to Example II.

FIG. 5 sets forth the NMR spectrum for the cis-3-hexenal producedaccording to Example II.

FIG. 6 sets forth the mass spectrum for cis-3-hexenal produced accordingto Example II.

FIG. 7 sets forth the NMR spectrum for trans-2-hexenal producedaccording to Example II.

FIG. 8 sets forth the mass spectrum for trans-2-hexenal producedaccording to Example II.

FIG. 9 sets forth the NMR spectrum for cis-3-hexenyl formate producedaccording to Example II.

FIG. 10 sets forth the mass spectrum for cis-3-hexenyl formate producedaccording to Example II.

FIG. 11 sets forth the NMR spectrum for cis-3-hexenyl-cis-3-hexenoateproduced according to Example II.

FIG. 12 sets forth the mass spectrum for cis-3-hexenyl-cis-3-hexenoateproduced according to Example II.

FIG. 13 sets forth the infrared spectrum forcis-3-hexenyl-cis-3-hexenoate produced according to Example II.

FIG. 14 sets forth the GLC profile for the cis-3-hexenyl-methyletherproduced according to Example III as separated on a GLC column (500ft.×0.03 in., SF 96 coated column; programmed at 80°-190° C. at 4° C.per minute) after distillation using a rotary evaporator.

FIG. 15 sets forth the GLC profile for cis-3-hexenyl-methylether astrapped out from the 500 ft.×0.03 in. SF-96 column programmed at80°-190° C. at 4° C. per minute.

THE INVENTION

It has now been determined that certain cis-3-hexenyl derivatives arecapable of imparting a variety of flavors and fragrances to variousconsumable materials and are also capable of augmenting or enhancing avariety of flavors and fragrances of various consumable materials.

Briefly, our invention contemplates augmenting or enhancing the flavorsand/or fragrances of such consumable materials as perfumes, perfumedarticles, colognes, foodstuffs, chewing gums, toothpastes, medicinalproducts and smoking tobaccos by adding thereto small but effectiveamount of at least one compound having the generic structure: ##STR5##wherein R is one of the moieties: ##STR6##

The cis-3-hexenyl derivatives of our invention augment or enhance sweet,deep green, fruity, pear-like, green apple-like, fresh fig-like, winey,white grape-like and crushed leaf flavor characteristics insofar asaugmenting or enhancing the aroma or taste of foodstuffs, toothpastes,medicinal products and chewing gums.

The cis-3-hexenyl derivatives of our invention also augment or enhancethe powerful green, leafy, fruity, fatty and spicy aromas and crushedgreen leaf undertones of perfumes, perfumed articles and colognes of ourinvention.

The cis-3-hexenyl derivatives of our invention also augment or enhancethe sweet, fruity, cooling and green aroma characteristics of smokingtobacco prior to and on smoking in both the mainstream and thesidestream.

Examples of the cis-3-hexenyl derivatives and mixtures thereof of ourinvention and their organoleptic characteristics are as follows:

                                      TABLE I                                     __________________________________________________________________________    Structure                  Flavor     Fragrance                               Mixture of      Compound or Mixture                                                                      Characteristics:                                                                         Characteristics:                                                                          Tobacco                     __________________________________________________________________________                                                      Characteristics:             ##STR7##       Mixture containing 33.1% cis-3-hexenal; 20.8% of trans-2-                     exenal; 5.5% of cis-3- hexenyl formate and 26.1% of                           cis-3- hexenyl-cis-3- hexenoate.                                                         Intense crushed green leaf aroma and taste                                    which is very long lasting; much longer                                       lasting than cis-3- hexenal taken alone and                                   examined previously.                                                                     Powerful green, fruity, fatty,                                                spicy aroma with leaf alcohol                                                 nuances and an intense very stable                                            natural green note. Stability about                                           100 times that of                                                                         A sweet, fruity,                                                              cooling green aroma                                                           prior to and on smoking                                                       in the mainstream and                                                         the side stream.             ##STR8##       Cis-3-hexenyl methyl ether.                                                              A sweet, green, fruity, pear, green                                           apple-like, fresh fig-like aroma and taste                                    characteristic at 1ppm. Suitable for fresh                                    fig, apple, peach and oral hygiene flavors.                                              Grassy, green aroma with fruit                                                topnote and jasmine-like                                                                  A sweet, fruity,                                                              cooling and green aroma                                                       haracteristic prior to                                                        and on smoking in both                                                        the mainstream and the                                                        sidestream.                 __________________________________________________________________________

Indeed the value of cis-3-hexenyl methylether has been demonstrated forvarious flavors:

A. In strawberry flavor cis-3-hexenyl methylether at 0.01% adds a freshfruit character both in aroma and taste.

B. In pineapple flavor cis-3-hexenyl methyl ether at 0.05% gives a freshpineapple character depressing the canned notes and creates asubstantially more pleasant and more intense aroma.

C. In peach flavor at 0.02% cis-3-hexenyl methyl ether imparts freshnessand a natural peach character of great intensity.

D. In peppermint oil (natural), cis-3-hexenyl methylether at the rate of0.05% gives an aroma lift, a fresher character both in aroma and taste.Indeed, cis-3-hexenyl methylether is essential in the creation ofartificial peppermint flavors and for oral hygiene products.

E. In raspberry flavor cis-3-hexenyl methylether at 0.01% adds andenhances the seedy/green kernel notes both in aroma and taste and roundsout the flavor making it fuller and more natural like.

An important aspect of this invention is the creation of crushed leafaroma and taste of a very high stability of a new composition of mattercontaining cis-3-hexenal. This composition of matter not only containscis-3-hexenal having the structure: ##STR9## but in addition containscis-3-hexenyl formate and/or cis-3-hexenol; and trans-2-hexenal; andcis-3-hexenyl cis-3-hexenoate. Trans-2-hexenal has the structure:##STR10## cis-3-hexenyl formate has the structure: ##STR11##cis-3-hexenyl cis-3-hexenoate has the structure: ##STR12## Thus, thequantities of substances in the composition of our invention whichcontains the cis-3-hexenal are as follows:

Cis-3-hexenal from 20% up to 80%;

Trans-2-hexenal from 5% up to 40%;

Cis-3-hexenyl formate from 0% up to 20%;

Cis-3-hexenol from 0% up to 40%;

Cis-3-hexenyl-cis-3-hexenoate from 1% up to 10%;

the percentages being "mole" percentages.

The foregoing mixture is useful in all fruit flavors, vegetable flavors,savory flavors and many others. This mixture can prepared by reactingcis-3-hexenol with pyridinium chlorochromate having the structure:##STR13## according to the reaction sequence: ##STR14## The mole ratioof cis-3-hexenol:pyridinium chlorochromate initially in the reactionmass may vary from 1:0.5 up to 1:2 with a preferred mole ratio ofcis-3-hexenol:pyridinium chlorochromate of 1:1.5. It is preferred thatthe reaction be carried out in a solvent such as methylene chloride. Theconcentration of cis-3-hexenol in the methylene chloride is from about0.2 up to about 1.5 moles per liter with a preferred concentration ofcis-3-hexenol in the methylene chloride of 0.5 M.

Cis-3-hexenol is also used to prepare the cis-3-hexenyl methylether byreaction of cis-3-hexenol with an etherifying agent such as sodiumhydride and methyliodide. The reactions can be carried out in thepresence of dimethylformamide or diethylbenzene according to thefollowing reaction scheme: ##STR15##

The reaction wherein cis-3-hexenol is oxidized to the composition ofmatter containing the cis-3-hexenal using the pyridinium chlorochromatemay be carried out also according to the conditions as specified in thepaper by Corey and Suggs, Tetrahedron Letters, No. 31, pages 2647-2650,1975 (Title: "Pyridinium Chlorochromate; an Efficient Reagent forOxidation of Primary and Secondary Alcohols to Carbonyl Compounds").

When the cis-3-hexenyl derivatives of our invention are used as foodflavor adjuvants, the nature of the co-ingredients included with saidcis-3-hexenyl derivatives in formulating the product composition willalso serve to alter, modify, augment or enhance the organolepticcharacteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms means "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks, andthe like.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine, and a flavoring composition whichincorporates one or more of the cis-3-hexenyl derivatives of ourinvention, and in addition, sweetening agents which may be sugars,including sucrose or dextrose and/or artificial sweeteners such ascyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising, broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like, and sequestrants, e.g., citricacid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids,carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like; buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike, firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alphamethylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutananl,beta,beta-dimethyl acrolein, methyl n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, 2-heptenal, nonyl aldehyde,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, beta-damascone, alpha-damascone,beta-damascenone, acetophenone, 2-heptanone, o-hydroxy-acetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methylfurfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpinhydrate, eugenol,linalool,2-heptanol, acetoin; esters, such as butyl acetate, ethyl acetate, ethylacetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethylcaproate, ethyl carpylate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethylmyristate, ethyl alpha-methylbutyrate, ethyl propionate, ethylsalicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate,hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate,methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate, and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyldiphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, alphaphellandrene, beta-phellandrene,p-cymene,1-alpha-pinene, beta-pinene, dihydrocarveol; pyrazines such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3 -dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oilssuch as jasmine absolute, cassia oil, cinnamon bark oil; black pepperoleoresin, oil of black pepper, rose absolute, orris absolute, oil ofcubeb, oil of coriander, oil of pimento leaf, oil of patchouli, oil ofnutmeg, lemon essential oil, safran oil, Bulgarian rose, capsicum, yarayara and vanilla; lactones such as gamma-nonalactone; sulfides, e.g.,methyl sulfide and other materials such as maltol, and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethyloxyethane and dimethoxymethane),piperine, chavicine, and piperidine.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the cis-3-hexenyl derivatives ofour invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with thecis-3-hexenyl derivatives of our invention and (iii) be capable ofproviding an environment in which the cis-3-hexenyl derivatives can bedispersed or admixed to provide a homogeneous medium. In addition,selection of one or more flavoring adjuvants, as well as the quantitiesthereof will depend upon the precise organoleptic character desired inthe finished product. Thus, in the case of flavoring compositions,ingredient selection will vary in accordance with the foodstuff, chewinggum, medicinal product or toothpaste to which the flavor and/or aromaare to be imparted, modified, altered or enhanced. In contradistinction,in the preparation of solid products, e.g., simulated foodstuffs,ingredients capable of providing normally solid compositions should beselected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofcis-3-hexenyl derivatives employed in a particular instance can varyover a relatively wide range, depending upon the desired organolepticeffects to be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored (e.g. with a grape flavor or an oral hygiene-type flavor) isrelatively bland to the taste, whereas relatively minor quantities maysuffice for purposes of enhancing the composition merely deficient innatural flavor or aroma. The primary requirement is that the amountselected be effective, i.e., sufficient to alter, modify or enhance theorganoleptic characteristics of the parent composition, whetherfoodstuff per se, chewing gum per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of one or more cis-3-hexenylderivatives of our invention will, of course, substantially vitiate anypossibility of obtaining the desired results while excess quantitiesprove needlessly costly and in extreme cases may disrupt theflavor-aroma balance, thus proving self-defeating. Accordingly, theterminology "effective amount" and "sufficient amount" is to be accordeda significance in the context of the present invention consistent withthe obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of cis-3-hexenyl derivativesranging from a small but effective amount, e.g., 0.05 parts per millionup to about 500 parts per million based on total composition, aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended since they fail to provide commensurateenhancement of organoleptic properties. In those instances wherein thecis-3-hexenyl derivatives are added to the foodstuff as an integralcomponent of a flavoring composition, it is of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective cis-3-hexenyl derivative concentration in thefoodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the cis-3-hexenyl derivatives inconcentrations ranging from about 0.025% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the cis-3-hexenyl derivatives with, forexamples, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a fruit-flavored powder mix, are obtained by mixing the driedsolid components, e.g., starch, sugar and the like, and cis-3-hexenylderivatives in a dry blender until the requisite degree of uniformity isachieved.

It is preferred to combine with the cis-3-hexenyl derivatives of ourinvention the following adjuvants: methyl anthranilate; ethylheptanoate; diethylmalonate; ethyl benzoate; ethyl butyrate; ethylacetate; benzyl acetate; peppermint oil; spearmint oil; clove oil;anethole; cardamon oil; oil of wintergreen; cinnamic aldehyde;heliotropine; benzaldehyde; paratoluacetaldehyde; vanillin;phenylacetaldehyde; benzyl acetate; maltol; benzylalcohol; andethyl-3-methyl-3-phenyl-glycidate.

The cis-3-hexenyl derivatives of our invention can be used to contributepowerful green, leafy, fruity, fatty and spicy aromas with powerfullong-lasting stable crushed green leaf nuances to perfumes, perfumedarticles and colognes. Examples of perfumed articles are anionic,cationic and nonionic detergents and dryer-added fabric softeners. Asolfactory agents the cis-3-hexenyl derivatives of our invention can beformulated into or used as components of a "perfume composition" or canbe used as components of a "perfumed article" or the perfume compositionmay be added to perfumed articles.

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones,nitriles, ethers, lactones, natural essential oils, synthetic essentialoils and frequently hydrocarbons which are admixed so that the combinedodors of the individual components produce a pleasant or desiredfragrance. Such perfume compositions usually contain: (a) the main noteor the "bouquet" or foundationstone of the composition; (b) modifierswhich round-off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and substances which retardevaporation; and (d) top-notes which are usually low-boiling,fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the individual compounds of this invention, ormixtures thereof, can be used to alter the aroma characteristics of aperfume composition, for example, by highlighting or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of the cis-3-hexenyl derivatives of this invention which willbe effective in perfume compositions depends on many factors, includingthe other ingredients, their amounts and the effects which are desired.It has been found that perfume compositions containing as little as 0.5%of the cis-3-hexenyl derivatives of this invention, or even less, can beused to impart an interesting green, leafy, fruity, fatty, spicy aromato soaps, liquid and solid cationic, anionic and nonionic detergents,cosmetics, powders, liquid and solid fabric softeners, opticalbrightener compositions, and other products. The amount employed canrange up to 50% higher and will depend on considerations of cost, natureof the end product, and the effect desired on the finished product andparticular fragrance sought.

The cis-3-hexenyl derivatives of this invention can be used alone or ina perfume composition as an olfactory component in detergents and soaps,space odorants and deodorants; colognes, toilet waters; bath salts; hairpreparations such as lacquers, brilliantines, pomades, and shampoos;cosmetic preparations such as creams, deodorants, hand lotions, and sunscreens; powders such as talcs, dusting powders, face powder, and thelike. When used as an olfactory component of perfumed article, as littleas 0.01% of one or more of the cis-3-hexenyl derivatives will suffice toimpart an interesting green, leafy, fruity, fatty, spicy aroma.Generally, no more than 0.5% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the cis-3-hexenyl derivatives alone or with other ingredients. Thevehicle can be a liquid such as an alcohol such as ethanol, a glycolsuch as propylene glycol, or the like. The carrier can be an absorbentsolid such as a gum or components for encapsulating the composition suchas gelatin which can be used to form a capsule wall surrounding theperfume oil as by means of coacervation.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired sweet,fruity, cooling and green notes. Such notes, both prior to and onsmoking, in both the main stream and the side stream, may now be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend; or the nature of thefilter used in conjunction with the smoking tobacco article.

This invention further provides improved tobacco additives and additivesfor materials used in the fabrication of tobacco articles (particularlysmoking tobacco articles) and methods whereby desirable sweet, fruity,cooling and green notes may be imparted to smoking tobacco products andmay be readily varied and controlled to produce the desired uniformflavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient, one ormore of the cis-3-hexenyl derivatives of our invention.

In addition to the cis-3-hexenyl derivatives of our invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with oneor more of the cis-3-hexenyl derivatives of our invention.

I. Synthetic Materials

Beta-methylcinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexen-1-ol;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-B)-furan;

4-Hydroxyhexenoic acid, gamma-lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil;

An aroma and flavoring concentrate containing one or more of thecis-3-hexenyl derivatives of our invention and, if desired, one or moreof the above-indicated additional flavoring additives may be added tothe smoking tobacco material, to the filter or to the leaf or paperwrapper or to a filter which is part of the smoking article. The smokingtobacco material may be shredded, cured, cased on blended tobaccomaterial or reconstituted tobacco material or tobacco substitutes (e.g.,lettuce leaves) or mixtures thereof. The proportions of flavoringadditives may be varied in accordance with taste, but insofar asenhancement or the imparting of sweet, fruit, cooling and green notesprior to and on smoking, in both the main stream and the side stream, wehave found that satisfactory results are obtained if the proportion byweight of the sum total of cis-3-hexenyl derivatives to smoking tobaccomaterial is between 50 ppm and 1500 ppm (0.005%-0.15%) of the activeingredients to the smoking tobacco material. We have further found thatsatisfactory results are obtained if the proportions by weight of thesum total of cis-3-hexenyl derivatives used to flavoring material isbetween 0.05:1 and 0.50:1.

Any convenient method for incorporating the cis-3-hexenyl derivatives inthe tobacco product may be employed. Thus the cis-3-hexenyl derivativestaken alone or along with other flavoring additives may be dissolved ina suitable solvent such as food grade ethanol, pentane, diethyl etherand/or other volatile organic solvents, and the resulting solution mayeither be sprayed on the cured, cased and blended tobacco material; orthe tobacco material or filter may be dipped into such solution. Undercertain circumstances, a solution of one or more cis-3-hexenylderivatives taken alone or taken further together with other flavoringadditives as set forth above, may be applied by means of a suitableapplicator such as a brush or roller on the paper or leaf wrapper forthe smoking product, or it may be applied to the filter by eitherspraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated, and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or morecis-3-hexenyl derivatives of our invention in excess of the amounts ofconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. As stated supra, the cis-3-hexenyl derivatives of our inventioncan be incorporated with materials such as filter tip materials, seampaste, packaging materials and the like which are used along with thetobacco to form a product adapted for smoking. Furthermore, thecis-3-hexenyl derivatives of our invention can be added to certaintobacco substitutes of natural or synthetic origin (e.g., dried lettuceleaves) and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption,by smoking or otherwise, whether composed of tobacco plant parts ofsubstitute materials or both.

It will thus be apparent that the cis-3-hexenyl derivatives of ourinvention can be utilized to alter, modify, augment or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following examples serve to illustrate our invention, and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of Composition Containing Cis-3-hexenal

REACTION: ##STR16##

Into a 500 ml, three-necked, reaction flask equipped with mechanicalstirrer, Friedrichs condenser and thermometer is placed 300 cc ofmethylene chloride and 19.0 grams of pyridine. While stirringvigorously, 12.0 grams of chromium trioxide are added over a 10-15minute period. The color of the mixture changes from yellow to darkpurple. When addition is about two thirds complete, the temperatureslowly begins to rise attaining a maximum of 34° C. by the time ofcompletion of addition. The reaction mixture is then stirred for 15minutes at room temperature. 2.0 Grams of cis-3-hexenol in about 2.0grams of methylene chloride is added in one portion. Stirring iscontinued for 15 minutes at room temperature. The reaction mixture isthen filtered (using a Buchner funnel with celite) and then throughsilica gel (using a sintered glass funnel of medium porosity). Almostall of the color is removed from the reaction mixture. The reactionmixture is then extracted with three 50 cc portions of one molarhydrochloric acid to remove residual pyridine. After drying the reactionmass is concentrated under nitrogen.

FIG. 1 is the GLC profile of the reaction mixture.

Analysis on an 8 ft.×1/8 in. 5% Carbowax column indicates the formationof a peak (13.6%) which is identified by mass spectral analysis ascis-3-hexenal.

The foregoing reaction is repeated using a 500 ml, three-necked reactionflask, equipped with mechanical stirrer, thermometer and additionfunnel.

184 ml of six molar hydrochloric acid is charged to a 500 mlthree-necked reaction flask equipped with a thermometer and mechanicalstirrer. 100 Grams (1 mole) of chromium trioxide is rapidly added withstirring. After five minutes the temperature is lowered to 0° C. using adry ice-isopropanol bath and 79.1 grams (1 mole) of pyridine iscarefully added over a 20 minute period. The temperature of the reactionmass rises to about 35° C. and the reaction mixture is again cooled to0° C. A yellow-orange solid separates. The yellow-orange solid iscollected on a Buchner funnel and dried over 90 minutes. It is thenplaced in vacuum for 90 minutes.

200 ml of methylene chloride and 32.3 grams (0.15 moles) of pyridiniumchlorochromate and 2.46 grams (0.03 moles) of sodium acetate are chargedto a 500 ml three-necked reaction flask equipped with mechanicalstirrer, thermometer and addition funnel.

10 Grams (0.1 moles) of cis-3-hexenol and 20 ml methylene chloride arethen added rapidly over a 2 minute period. The reaction mixture is thenstirred for a period of 15 minutes during which time the temperature isallowed to rise reaching a maximum of 40° C. The resulting liquid isdecanted and the residue is washed with diethylether. The combinedorganic layers are then filtered through silica gel on a sintered glassfunnel, dried and concentrated. The GLC profile indicates 61.0%cis-3-hexenal and 29.5% of cis-3-hexenol. Removal of most of the solventyields 6.14 grams of which 31.3% is cis-3-hexenal and 19.4% iscis-3-hexenol.

EXAMPLE II Preparation of Composition Containing Cis-3-hexenal in StableForm

REACTION: ##STR17##

Into a 1000 ml three-necked reaction flask equipped with mechanicalstirrer, thermometer, addition funnel, dry ice-isopropanol bath andcondenser is placed 368 cc of six molar hydrochloric acid. To thehydrochloric acid is added 200 grams (2 moles) of chromium trioxide,rapidly, with stirring. After 5 minutes the reaction mixture is cooledto 0° C. and 158.2 grams (2 moles) of pyridine is added over a period of20 minutes. The reaction mass is cooled to 0° C. and a yellow-orangesolid is obtained which is collected on a sintered glass funnel undermaximum house vacuum. Suction is maintained until no more liquidfiltrate is obtained (2.5 hours).

323 Grams of the pyridinium chlorochromate thus obtained are added to2000 ml methylene chloride. 100 Grams of cis-3-hexenol in 100 cc ofmethylene chloride are added to the reaction mass. The resulting mixtureturns black and a solid separates. The reaction temperature rises to 40°C. over a period of 15 minutes and begins to reflux. The progress of thereaction is monitored by GC indicating the following reaction products:

    ______________________________________                                        Time    Cis-3-Hexenal                                                                             Trans-2-Hexenal                                                                            Cis-3-Hexenol                                ______________________________________                                         2 minutes                                                                             8.7%       3.2%         87.1%                                        25 minutes                                                                            35.0%       9.5%         37.8%                                        40 minutes                                                                            37.0%       15.9%        26.6%                                        ______________________________________                                    

The reaction mass is then quenched by cooling to 25° C. with wet ice. Itis then filtered through Celite (100 grams). The reaction flask isrinsed with two 50 cc diethylether portions and the filtrate is filteredthrough 100 grams of silica gel. The filtrate is dried and concentrated.The conversion to and yield of cis-3-hexenal is 26.0% conversion and32.8% yield.

The 81.32 grams of crude product is placed on a 500 gram column of 5%water-deactivated silica gel and eluted with 2 liters of 20%diethylether:hexane. 24.8 Grams of product are obtained and itscomposition is as follows:

Cis-3-hexenal 33.1%;

Trans-2-hexenal 20.8%;

Cis-3-hexenol 26.1%;

Cis-3-hexenyl-cis-3-hexenoate 2.7%

Cis-3-hexenyl formate 12.7%

This sample has interesting highly stable light green crushed leaf notesat 0.01 ppm. Compared with trans-2-hexenal at 0.1 ppm both materials arecompletely different with mixture containing the cis-3-hexenal beingmuch more powerful and the trans-2-hexenal being very weak. The applejuice aroma is intense and unique.

FIG. 2 sets forth the GLC profile of the reaction mass. FIG. 3 setsforth the NMR spectrum for the cis-3-hexenol. FIG. 4 sets forth the massspectrum for the cis-3-hexenol. FIG. 5 sets forth the NMR spectrum forthe cis-3-hexenal in the mixture. FIG. 6 sets forth the mass spectrumfor the cis-3-hexenal in the mixture. FIG. 7 sets forth the NMR spectrumfor the trans-2-hexenal in the mixture. FIG. 8 sets forth the massspectrum for the trans-2-hexenal in the mixture. FIG. 9 sets forth theNMR spectrum for the cis-3-hexenyl formate in the mixture. FIG. 10 setsforth the mass spectrum for the cis-3-hexenyl formate in the mixture.FIG. 11 sets forth the NMR spectrum for thecis-3-hexenyl-cis-3-hexenoate in the mixture. FIG. 12 sets forth themass spectrum for the cis-3-hexenyl-cis-3-hexenoate in the mixture. FIG.13 sets forth the infrared spectrum for thecis-3-hexenyl-cis-3-hexenoate in the mixture.

EXAMPLE III Preparation of Cis-3-hexenyl Methyl Ether

REACTION: ##STR18##

250 ml of Dimethyl formamide and 24 grams (50% in mineral oil, 0.5moles) of sodium hydride are charged to a one liter reaction flaskequipped with mechanical stirrer, heating mantle, thermometer andstoppered addition funnel. Cis-3-hexenol (50 grams, 0.5 moles) is slowlyadded over a period of 30 minutes to the reaction mass. During theaddition the reaction mass exotherms to 40° C. The reaction mass isheated slightly. When the reaction is finished the reaction mass iscooled to room temperature and 78.1 grams (0.55 moles) of iodomethane isadded. The reaction mass is then heated slowly to reflux and monitoredby GLC. (500 ft.×0.03 in. SF-96 column programmed at 80°-190° C. at 4°C. per minute). When GLC indicates that no more reaction is taking place(that is when the iodomethane is used up) the reaction mass is cooled toroom temperature and slowly poured into 500 ml of water.

The reaction product is extracted with anhydrous diethyl ether and theextract is dried over anhydrous sodium sulfate and concentrated using arotary evaporator. Spectral data confirmed that the resulting product iscis-3-hexenyl methyl ether.

FIG. 14 sets forth the GLC profile of the reaction mixture afterobtention from the rotary evaporator (conditions: 500 ft.×0.03 in. SF-96column programmed at 80°-190° C. at 4° C. per minute). FIG. 15 setsforth the GLC profile of the trapped material, the cis-3-hexenyl methylether (conditions: 10 ft.×1/8 in. SE 30 column programmed at 70°-190° C.at 10° C. per minute).

EXAMPLE IV Preparation of Cis-3-hexenyl Methyl Ether Using DiethylBenzene Solvent

Into a 3 liter reaction flask equipped with mechanical stirrer, heatingmantle, Claisen adaptor, thermometer, Friedrichs condenser and additionfunnel is placed 132 grams of sodium hydride (50% in mineral oil) (2.75moles) and 1 liter of diethyl benzene. 200 Grams (2 moles) ofcis-3-hexenol is then added dropwise over a period of one hour while thereaction mass exotherms to 43° C. The reaction mass is then refluxed at120° C. for 30 minutes. The reaction mixture bubbles hydrogen offvigorously.

When there appears to be no more gas given off the reaction mass iscooled to room temperature.

312.4 Grams (2.2 moles) of iodomethane is added dropwise over a periodof one hour. The reaction mass is then heated over a period of two hoursat reflux 120°-145° C. The reaction mass is then cooled to roomtemperature and added with stirring to two liters of water. Thewater/reaction mass mixture is then stirred for one hour. The reactionmass is then added to a 4 liter separatory funnel and the organic layeris separated from the aqueous layer. The organic layer is set aside andthe aqueous layer is filtered through a Buchner funnel and extractedtill odorless with five 300 ml portions of diethyl ether. The diethylether is then removed on a rotary evaporator and the extract is added tothe organic layer that was set aside. The resulting organic phase isdried over anhydrous sodium sulfate and a GC analysis indicates that1.43 % of cis-3-hexenol remains. The resulting product (867.3 grams) isplaced in a 2 liter distillation flask adding 25 grams of triethylborate and the product rush-over distilled on a 14 inch column at 760mmHg til the pot temperature reaches 150° C.

The mixture that is left in the pot is transferred to a fractionaldistillation set up yielding the following fractions:

    ______________________________________                                                                         Weight of                                    Fraction No.                                                                            Vapor Temp.                                                                              Liquid Temp.                                                                              Fraction                                     ______________________________________                                        1         25/33      25/81                                                    2         33         83                                                       3         33         82               5.2                                     4         34         83                                                       5         35/39      83               5.1                                     6         37         83               1.7                                     7         37         83               5.8                                     8         37         83               2.7                                     9         37         84               2.2                                     10        37         84               4.3                                     11        37/39      85               7.3                                     12        37         85               7.5                                     13        36         85               10.8                                    14        37         85               2.3                                     15        37         84               5.3                                     16        37         95               8.7                                     17        38         105              4.6                                     18        38         115              3.8                                     19        25/37      125              2.8                                     20        37         125              5.8                                     21        37         128              3.5                                     22        38         128              6.2                                     23        38         128              3.4                                     24        38         129              6.5                                     25        38         130              4.3                                     26        37         130              4.0                                     27        35         130              5.3                                     28        31         130              Trace                                   ______________________________________                                    

Fractions 5-27 are bulked and evaluated. Fractions 5-27 bulked have asweet, green, fruity, pear, green apple-like and fresh fig aroma andtaste at the level of 1 ppm.

EXAMPLE V Grape Flavor Containing Cis-3-hexenal

The following basic grape flavor formulation is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Methylanthranilate  8                                                         Ethylheptanoate     1                                                         Diethylmalonate     4                                                         Ethylbenzoate       1                                                         Ethylbutyrate       20                                                        Ethylacetate        35                                                        Benzylacetate       1                                                         Benzylalcohol       5                                                         Propylene glycol    25                                                        ______________________________________                                    

This basic grape flavor formulation is divided into two parts, to thefirst part 0.2% by weight of the composition of matter preparedaccording to Example II containing cis-3-hexenal is added, to the secondpart nothing is added. Fresh topnotes are present in the flavorcontaining the composition of Example II, with a significant increase inthe pulpy, skin notes. The total flavor is more natural juice like usingthe composition of Example II. Therefore, the flavor with thecomposition of Example II containing the cis-3-hexenal is preferred byall members of a four member bench panel.

EXAMPLE VI Use of Cis-3-hexenyl Methyl Ether in a Basic Oral HygieneFlavor

The following basic oral hygiene flavor is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Peppermint oil      89.0                                                      Spearmint oil       2.0                                                       Clove oil           1.0                                                       Anethole            2.0                                                       Cardamom oil        0.1                                                       Wintergreen oil     5.0                                                       Cinnamic aldehyde   0.9                                                       ______________________________________                                    

This basic oral hygiene flavor is compared in water at the rate of 8 ppmwith and without the addition of 2 ppm of cis-3-hexenyl methyl etherprepared according to Example III or Example IV. The ethereal characterof cis-3-hexenyl methyl ether prepared according to Example III or IVfound in the flavor with the addition of this chemical does not onlycreate the impression of a stronger flavor but a mouth coating effectextends the flavor impact and increases the cooling effect. In addition,the flavor with the cis-3-hexenyl methyl ether is longer lasting.Therefore, the flavor with the cis-3-hexenyl methyl ether is preferredby a bench panel of four members.

EXAMPLE VII Use of Cis-3-hexenyl Methyl Ether in a Basic CherryFormulation

The following basic cherry flavor formulation is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Heliotropine        10.0                                                      Benzaldehyde        5.0                                                       Paratoluacetaldehyde                                                                              0.5                                                       Vanillin            2.0                                                       Ethyl-3-methyl-3-phenyl                                                                           4.0                                                       glycidate                                                                     Phenylethylacetaldehyde                                                                           0.1                                                       Benzylacetate       0.2                                                       Maltol              2.0                                                       Benzylalcohol       6.2                                                       Propylene glycol    70.0                                                      ______________________________________                                    

The basic cherry flavor is compared in water at the rate of 20 ppm withand without the addition of 0.02 ppm of cis-3-hexenyl methyl etherprepared according to Example III or IV. The flavor with thecis-3-hexenyl methyl ether has a more black cherry juice character bothin aroma and taste. Therefore, it is preferred by a bench panel as beingmore natural and more characteristic.

EXAMPLE VIII Perfume Formulations Containing Cis-3-hexenal andCis-3-hexenyl Methyl Ether

The following basic jasmine formulations are prepared:

    ______________________________________                                                         Parts by Weight                                              Ingredients        8A         8B                                              ______________________________________                                        Benzyl Acetate     30.0       30.0                                            Phenyl Ethyl Alcohol                                                                             20.0       20.0                                            Eugenol            0.2        0.2                                             Geraniol           2.0        2.0                                             Benzyl Alcohol     20.2       20.2                                            Linalool           5.0        5.0                                             Indole-10% in Diethyl                                                         phthalate          0.5        0.5                                             Ylang Ylang Oil    0.1        0.1                                             Isophytol          10.0       10.0                                            Jasmine Absolute   1.0        1.0                                             Amyl Cinnamic Aldehyde                                                                           5.0        5.0                                             Benzyl Propionate  5.0        5.0                                             Composition containing                                                        Cis-3-hexenal produced                                                        according to Ex. II                                                                              1.0        --                                              Cis-3-hexenyl methyl                                                          ether produced according                                                      to Example III or IV                                                                             --         1.0                                             ______________________________________                                    

The intense green, leafy character of the cis-3-hexenal compositionproduced according to Example II or the cis-3-hexenyl methyl etherproduced according to Example III or IV fits well into the jasminetopnote enhancing and making the formulations much more natural like andlonger lasting.

EXAMPLE IX A. Powder Flavor Formulation

20 Grams of the flavor composition of Example V is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Liquid Grape Flavor                                                           Composition of Ex. V   20                                                     Propylene glycol       9                                                      Cab-O-Sil® M-5     5.00                                                   (Brand of Silica produced by the                                              Cabot Corporation of 125 High St.,                                            Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface Area: 200m.sup.2 /gm                                                  Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.                                                       ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid grape flavor composition ofExample V with vigorous stirring, thereby resulting in a viscous liquid.71 Parts by weight of the powder flavor composition of Part A, supra, isthen blended into the said viscous liquid, with stirring, at 25° C. fora period of 30 minutes resulting in a dry, free flowing sustainedrelease flavor powder.

EXAMPLE X

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of Example Vis added to the solution which is then homogenized to form an emulsionhaving particle size typically in the range of 2-5 microns. Thismaterial is kept at 120° F. under which conditions the gelatin will notjell.

Coascervation is induced by adding slowly and uniformly 40 parts byweight of a 20 % aqueous solution of sodium sulphate. Duringcoascervation the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7 % aqueous solution of sodium sulphate at 65° F. Theresulting jelled coascervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37 % solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XI Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example IX. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastinggrape flavor.

EXAMPLE XII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example X. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastinggrape flavor.

EXAMPLE XIII A. Power Flavor Formulation

20 Grams of the flavor composition of Example VI is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Oral Hygiene Flavor                                                           Composition of Ex. VI  20                                                     Propylene glycol       9                                                      Cab-O-Sil® M-5     5.00                                                   (Brand of Silica produced by the                                              Cabot Corp. at 125 High Street,                                               Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.                                                       ______________________________________                                    

The Cab-O-Sil is dispersed in the oral hygiene flavor composition ofExample VI with vigorous stirring, thereby resulting in a viscousliquid. 71 Parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring, at25° C. for a period of 30 minutes resulting in a dry, free flowingsustained release flavor powder.

EXAMPLE XIV

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleVI is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coascervation is induced by adding slowly and uniformly 40 parts byweight of a 20 % aqueous solution of sodium sulphate. Duringcoascervation the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelation is effected by pouring the heated coascervate mixture into1,000 parts by weight of 7 % aqueous solution of sodium sulphate at 65°F. The resulting jelled coascervate may be filtered and washed withwater at temperatures below the melting point of gelatin, to remove thesalt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37 % solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE XV Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XIII. Mixing is effected in aribbon blender with jacketed side walls of the type manufactured by theBaker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingoral hygiene flavor.

EXAMPLE XVI Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XIV. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingoral hygiene flavor.

EXAMPLE XVII Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight  Ingredients                                                  ______________________________________                                        Group "A"                                                                     30.200           Glycerine                                                    15.325           Distilled water                                               .100            Sodium Benzoate                                               .125            Saccharin Sodium                                              .400            Stannous Fluoride                                            Group "B"                                                                     12.500           Calcium Carbonate                                            37.200           Dicalsium Phosphate                                                           (Dihydrate)                                                  Group "C"                                                                     2.000            Sodium N-Lauroyl                                                              Sarcosinate (foaming                                                          agent)                                                       Group "D"                                                                     1.200            Flavor material of                                                            Example XIII                                                 100.00 Total                                                                  ______________________________________                                    

PROCEDURE:

1. The ingredients in Group "A" are stirred and heated in a streamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed

4. With stirring, the flavor of "D" is added and lastly thesodium-n-lauroyl sarcosinate

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal tooth-brushing procedureyields a pleasant oral hygiene flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XVIII Chewable Vitamin Tablets

The flavor material produced according to the process of Example XIII isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                             Gms/1000 Tablets                                         ______________________________________                                        Vitamin C (ascorbic acid) as                                                  ascorbic acid-sodium ascorbate                                                mixture 1:1            70.11                                                  Vitamin B.sub.1 (thiamine mononitrate)                                        as Rocoat® thiamine mononitrate                                           331/3% (Hoffman La Roche)                                                                            4.0                                                    Vitamin B.sub.2 (riboflavin) as                                               Rocoat® riboflavin 331/3%                                                                        5.0                                                    Vitamin B.sub.6 (pyridoxine hydrochloride)                                    as Rocoat® pyridoxine hydrochloride                                       331/3%                 4.0                                                    Niacinamide as Rocoat® niacinamide                                        331/3%                 33.0                                                   Calcium pantothenate   11.5                                                   Vitamin B.sub.12 (cyanocobalamin) as                                          Merck 0.1% in gelatin  3.5                                                    Vitamin E (dl-alpha tocopheryl                                                acetate) as dry Vitamin E acetate                                             331/3%                 6.6                                                    d-Biotin               0.044                                                  Flavor of Example XIII (as indicated above)                                   Certified lake color   5.0                                                    Sweetener - sodium saccharin                                                                         1.0                                                    Magnesium stearate lubricant                                                                         10.0                                                   Mannitol q.s. to make  500.0                                                  ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slus to 14 mesh. 13.5 Grams dry Vitamin A Acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 gm each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong oral hygiene flavor for a period of 12 minutes.

EXAMPLE XIX

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Bright             40.1                                                       Burley             24.9                                                       Maryland           1.1                                                        Turkish            11.6                                                       Stem (flue cured)  14.2                                                       Glycerine          2.8                                                        Water              5.3                                                        ______________________________________                                    

The above tobacco is used in producing cigarettes, and the followingformulation is compounded and incorporated into each of thesecigarettes:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Ethyl butyrate     .05                                                        Ethyl valerate     .05                                                        Maltol             2.00                                                       Cocoa extract      26.00                                                      Coffee extract     10.00                                                      Ethyl alcohol      20.00                                                      Water              41.90                                                      ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with the mixture produced according to Example II at 100ppm per cigarette. Another one-third of these model cigarettes aretreated in the filter with cis-3-hexenyl-methyl-ether produced accordingto Example III at the rate of 2×10⁻⁵ gm. When evaluated by pairedcomparison, the cigarettes treated both in the tobacco and in the filterwith the compositions, respectively, of Example II and Example III arefound, in smoke flavor, to be more tobacco-like with sweet, fruity,cooling, green aromas prior to and on smoking in the mainstream and inthe sidestream.

EXAMPLE XX Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talciumpowder with 0.25 g of the composition of matter as set forth in thetable below. Each of the cosmetic powders prepared with each of theingredients of the composition of matters set forth in the table belowhas an aroma as set forth in the table below:

A. Mixture of Example II:

Powerful green, fruity, fatty, spicy aroma with leaf alcohol nuances andan intense very stable natural green note.

B. Cis-3-Hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

EXAMPLE XXI Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976) with aromas as indicated in the table below areprepared containing 0.10%, 0.15% and 0.20% of the compositions of matteras set forth in the table below. They are prepared and added byhomogeneously mixing the appropriate quantity of fragrance compositionsas set forth in the table below in the liquid detergent. The detergentsall possess excellent aromas as set forth in the table below withgreater concentrations of perfume composition:

A. Mixture of Example II:

Powderful green, fruity, fatty, spicy aroma with leaf alcohol nuancesand an intense very stable natural green note.

B. Cis-3-hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

EXAMPLE XXII Preparation of a Cologne and Handkerchief Perfume

The compositions as set forth in the table below are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% and 85%, 90%, and 95% aqueous food grade ethanol; and intohandkerchief perfumes at concentrations of 15%, 20%, 25%, 30% and 40%(in 85%, 90% and 95% aqeuous food grade ethanol). Distinctive aromas asset forth in the table below are imparted to the colognes and to thehandkerchief perfumes as all levels indicated above:

A. Mixture of Example II:

Powerful green, fruity, fatty spicy aroma with leaf alcohol nuances andan intense very stable natural green note.

B. Cis-3-Hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

EXAMPLE XXIII Preparation of Soap Compositions

One hundred grams of soap chips are mixed with one gram of each of theformulations as set forth in the table below until homogeneouscompositions are obtained. In each of the cases, the homogeneouscompositions are heated under three atmospheres pressure at 180° C. fora period of three hours and the resulting liquids are placed into soapmolds. The resulting soap cakes on cooling manifest aromas as set forthbelow;

A. Mixture of Example II:

Powerful green, fruity, fatty spicy aroma with leaf alcohol nuances andan intense very stable natural green note.

B. Cis-3-Hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

EXAMPLE XXIV Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I:

    ______________________________________                                                           Percent by Weight                                          ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                        12                                                       Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water brighteners                                                                  q.s.                                                     ______________________________________                                    

The detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 grams of each of the materials asset forth in the table below. Each of the detergent samples hasexcellent aromas as set forth in the table below:

A. Mixture of Example II:

Powerful green, fruity, fatty spicy aroma with leaf alcohol nuances andan intense very stable natural green note.

B. Cis-3-Hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

EXAMPLE XXVI

Utilizing the procedure of Example I of column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate as a dryer-added fabric softeningarticle a manufacture is prepared wherein the substrate, the substratecoating and the outer coating and the perfuming material are as follows:

1. a water "dissolvable" paper (Dissolvo Paper);

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of the composition of matter as set forth in the table belowgiving rise to the aroma nuances as set forth in the table below:

A. Mixture of Example II:

Powerful green, fruity, fatty spicy aroma with leaf alcohol nuances andan intense very stable natural green note.

B. Cis-3-Hexenyl-Methyl-Ether produced according to Example III:

A grassy, green aroma with fruity topnotes and a jasmine-like undertone.

C. Compositions of Example VIII:

Intense green, leafy aroma with strong jasmine topnote.

A fabric softening composition prepared as set forth above having theabove aroma characteristics essentially consists of a substrate having aweight of about 3 grams per 100 square inches, a substrate coating ofabout 1.85 grams per 100 square inches of substrate and an outer coatingof about 1.4 grams per 100 square inches of substrate, thereby providinga total aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate. The aroma as set forth above is imparted ina pleasant manner to the head space in the dryer on operation thereofusing said dryer added fabric osftening nonwoven fabric.

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a solid or liquid anionic, cationic or nonionic detergent comprisingthe step of intimately admixing with a solid or liquid anionic, cationicor nonionic detergent base from 0.01% up to 0.5% of at least onesubstance selected from the group consisting of:A. A composition ofmatter consisting essentially of cis-3-hexenal,cis-3-hexenyl-cis-3-hexenoate, trans-2-hexenal, and cis-3-hexenol; B. Acomposition of matter consisting essentially of cis-3-hexenal,cis-3-hexenyl-cis-3-hexenoate, cis-3-hexenyl formate andtrans-2-hexenal; C. A composition of matter consisting essentially ofcis-3-hexenal, cis-3-hexenyl-cis-3-hexenoate, cis-3-hexenol,cis-3-hexenyl formate and trans-2-hexenal; and D. Cis-3-hexenyl methylether.